US2006541A - Manufacture of aliphatic - Google Patents

Description

Patented July 2, 1935 a 1 UNITED STATES, PiA'lENT'OFFlCE MANUFACTURE OF :ALIPHATIC ANHYDRIDES Henry Dreyfus, London, England 7 N0 Drawing. Application May 25, 1929, Serial No. 366,096. In Great Britain June 7, 1928 ,22 Claims. (01. 260 -123) This invention relates to the manufacture of n t ad Of fi st mi the phenols aliphatie aliphatic anhydrides from aliphatic. acids and acid esters of phenols with the aliphatic acid especially to the manufacture of acetic anhy ap y, for t c inject the phenol dride from acetic acid. aliphatic acid;esters:of phenol directly, in liquid It is known that aliphatic anhydrides can be r vap r f m, in t h a e r i n Zone, prepared by subjecting vaporsof aliphatic acids t IOHgh Which the'aliphatic acid Vapor is Caused to thermal decomposition and various catalysts to pass. in. a rapid stream. have been proposed for the reaction, It is to be understood that the invention is not I have now found that phenols and their alil mited'as t0 th p S p y as the l phatic acid esters are highly useful catalysts for ess of the invention may be performed under orthe reaction. dinary atmospheric pressure, or under reduced According to the invention therefore I propressure or vacuum or under hi pressures duce aliphatic anhydrides (and especially acetic than atmospheric, for instance, under pressures anhydride) by subjecting vapors of aliphatic of from 3 to 10 atmospheres or more.

acids (and especially acetic'acid) to thermal do The an yd e pr u ed y the process may be composition in presence of one or more phenols separated from the reaction gases or vapors in or aliphatic acid esters of phenols. any suitable Way. Theanhydride separated or In performing the invention I preferably emrecovered from the reaction gases or vapors may ploy one or more of the following phenols or if desired or req p fi by y Suitable aliphatic acid esters of phenols:-phenol, one or means. For instance, it may be distilled from more cresols or xylenols, or acetates of such an anhydrous acetate .(e. g. anhydrous sodium phenols, though it is of course understood that I acetate). in no wise limit myself to these particular e:;- In the recovery or separation of the anhydride amples, from the reaction vapors the reaction gases or The reaction may be performed at tempera Vapors are preferably not submitted to simple tures of from about 250 to 1000 C. and prefercondensation as such condensation involves hyably at temperatures of from about 300;to drolysis and consequent loss of anhydride, but 700 C. I they are preferably treated to separate the an- The reaction may be performed in any conhydride from the water vapor present or formed venient manner. For instance, a mixture of in the reaction. For instance, the gases or vapors D acetic acid or other aliphatic. acid and one or from the-reaction zone may be subjected to fracmore phenols or aliphatic acid esters of phenols tional condensation for example by leading them may be passed in vapor form in a rapid stream up through one or more fractionating columns through a reaction zone heated to the desired maintained ata temperature or temperatures-intemperature. Such reaction zone may be formed termediate between the. boiling points (under the from tubes (or other form of apparatus) made conditions offlpressure obtaining) of the anhyfrom or lined with copper, silica, earthenware dride and of water, whereby the anhydride is or other suitable material and may, if desired, condensed and the water passes on in vapor form. be filled with or otherwise contain, balls, granules Or, for instance, the reaction gases or vapors or pieces of pumice, kieselguhr, carborundum or may, if desired, be passed through one or more other filling materials. Further if desired, the solventsfor theanhydride which are insoluble reaction zone may contain catalysts hitherto in water and which have higher boiling points known to promote the scission of aliphatic acids than water (preferably of higher boiling point into their anhydrides. 7 than the anhydride). such solvents being em- The mixtures of the aliphatic acids and the ployed at temperatures intermediate between the phenols or aliphatic acid esters of phenOlsmay boiling points (under the conditions of pressure be made in any suitable way. Conveniently they obtaining) of Water and of the anhydridewheremay be prepared by simple admixture in the vaby the anhydride is condensed or absorbed and per form or by passing vapors of the aliphatic the water escapes in vapor form. As examples of acid in a regulated stream through the hot or such. solvents may be mentioned chlorbenzene,

boiling phenols or aliphatic acid esters ofphenols; paradichlorbenzene, benzylether, tetrachloreth- In p rfo m n the reaction I pr f ly mpl y ane, paraflin oil, triacetin, phenetol, anisol', one mixtu es Containing out to'10% of the or more cresols, and paracresyl acetate. phenols or aliphatic acid esters of phenols, though Or, for instance, the reaction gases or vapors I in no wise limit myself in thisrespect. may, if desired, be subjected to condensation by the process described in U. S. application S. No. 284,566 filed June 11, 1928, that is to say the anhydride may be condensed from the reaction vapors whilst carrying away the water vapor by the vapor of one or more entraining liquids. In such form of execution the reaction vapors are preferably mixed, after leaving the reaction zone, with the vapors of the entraining liquid or liquids at a temperature below the boiling point (under the conditions of pressure obtaining) of the anhydride. Conveniently such mixing may be performed by introducing the reaction vapors (which should not be allowed to cool below the-boiling point of water before becoming mixed with the vapors of the entraining liquid or liquids) into a vessel up which the vapors of' the entraining liquid or liquids are caused to rise; by this means the anhydride may be substantially condensed and the water vapor carried away with the vapors of the entraining liquid or liquids. Examples of entraining liquids which I may use for such method of condensation are benzene, carbon tetrachloride, petrol, mixtures of two or more of such bodies, or mixturesv of ether with petroleum ether; it will be understood, however, that any other liquids chemically inert to the anhydride and having a high entraining capacity for water may be employed. The liquid should preferably have a low entraining capacity forthe anhydride. Entraining liquids. such as toluol, xylenes or otherentraining liquids whose boiling points are intermediate between those of water and of the anhydride, are especially suitable for this method of separation.

Or, again for instance, the reaction gasesor vapors may be subjected to condensation by the process described in U. S. application S. No. 285,613 filed June 15, 1928, that is to say they may be subjected to condensation by leading them under the surface of an extracting liquid cooled down or otherwise kept at temperatures below (and preferably considerably below) the boiling point of water. By the term extracting liquid is meant a liquid or liquid mixture in which the anhydride is soluble and. which is chemically inert to the anhydrideand insoluble or substantially insoluble in .water. As examples of such extracting liquids may be mentioned benzene, chloroform and mixtures of ethyl ether or chloroform with one or more hydrocarbons such as light paraffins, gasoline, kerosene, benzol or its homologues. It is preferable to use as extracting liquids, liquids of the character referred to which are themselves hydrocarbons or which contain hydrocarbons, for example, benzene or mixtures of ethyl ether or chloroform with one or'more hydrocarbons such as parafilns (particularly the petroleum fraction of boiling point 40 to '1 0 C. termed petroleum ether), gasoline (boiling point 70 to C.), kerosene, benzol or its homologues. The following particular examples of extracting liquids are very suitable 1- ether in admixtures with petroleum ether, chloroform mixed with petroleum ether and/or gasoline; and mixtures of ether and petroleum ether containing about 30 to 50% petroleum ether are especially suitable.

Or again, for instance, the reaction vapors may be treated by the process described in my U. S. application S. No. 242,977 filed December 27, 1927, that'is to say they may be passed over or otherwise in contact with one or more water binding substances maintained at a temperature or temperatures below (and preferably substantially below) the temperature at which the reaction vapors are produced. By such treatment the water vapor may be substantially absorbed from the reaction vapors. In such treatment the water binding substances are preferably maintained at temperatures above the boiling point (under the conditions of pressure obtaining) of water to avoid condensation of water and resulting risk of loss of anhydride through hydrolysis, and for the best functioning of the treatment the water binding substances should be employed at temperatures above the boiling point of the anhydride in which case the water can besubstantially absorbed and the anhydride pass on in vapor form. The term water binding substances means bisulphates, pyrosulphates (especially bisulphates and pyrosulphates of the alkali and earth alkali metals), zinc chloride, calcium chloride, orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid and like substances which have affinity (and preferably high affinity) for water but excludingsubstances having a deleterious effect on aliphatic acids or anhydrides such as sulphuric acid.

Or again, for instance, the reaction vapors may be subjected to condensation by the process described in previous U. S. application S. No. 330,577 filed January 5, 1929, that is to say they may be caused to impinge upon a flowing stream of benzene (or other water insoluble solvent for the anhydride) whereby the gases or vapors are quickly cooled and condensed and the anhydride separated from the water. The benzene (or other solvent) so employed may be collected and the water layer (usually the lower layer) which separates out may be removed and the benzene 1 (or equivalent) layer distilled to recover the anhydride.

In cases where the thermal decomposition of the aliphatic acid vapor is performed under pressure higher than atmospheric it is preferable, prior to subjecting the reaction gases or vapors to treatment for recovery or separation of the anhydride, to pass the reaction gases or vapors through one or more reducing valves or like apparatus in order to reduce the pressure substantially to atmospheric.

It is to be understood that the invention is not limited as to the strength of aliphatic acid employed. The process can be performed even with the vapors of dilute acids; and besides affording a ready means for the manufacture of anhydrides from concentrated or highly concentrated acids, it affords valuable means for producing anhydrides from waste or dilute acids, especially waste or dilute acids such as result from the acetylation of cellulose or other industrial acetylation processes.

The following example serves to illustrate a convenient form of execution of the invention it being understood that it is given solely by way of example.

Example A mixture of the vapors of phenol and acetic acid, containing about 5% of phenol is passed in a rapid stream through an earthenware tube which is filled with balls or stones of pumice and heated to a temperature between 400 and 600 C. The vapors leaving the heated tube are subjected to fractional condensation by leading them upwards through one or more fractionating columns maintained at a temperature or temperatures intermediate between the boiling points of acetic anhydride and of water, whereby the anhydride is substantially condensed and the water allowed to pass on in vapor form.

What I claim and desire to secure by Letters Patent is:-

1. Process for the manufacture of an aliphatic anhydride, which comprises subjecting the vapor of an aliphatic acid to thermal decomposition in presence of at least one body selected from the group consisting of phenols of the benzene series and their lower aliphatic acid esters.

2. Process for the manufacture of an aliphatic anhydride, which comprises subjecting the vapor of an aliphatic acid to thermal decomposition in presence of a monohydric phenol of the benzene series.

3. Process for the manufacture of an aliphatic anhydride which comprises subjecting the vapor of an aliphatic acid to thermal decomposition in presence of phenol.

4. Process for the manufacture of an aliphatic anhydride, which comprises subjecting the vapor of an aliphatic acid to thermal decomposition in presence of a lower aliphatic acid ester of a monohydric phenol of the benzene series.

5. Process for the manufacture of an aliphatic anhydride, which comprises subjecting thevapor of an aliphatic acid to thermal decomposition in presence of a lower aliphatic acid ester of phenol.

6. Process for the manufacture of an aliphatic anhydride, which comprises subjecting the vapor of an aliphatic acid to thermal decomposition in presence of phenol acetate.

7. Process for the manufacture of an aliphatic anhydride, which comprises subjecting to thermal decomposition a vaporous mixture comprising an aliphatic acidand a monohydric phenol of the benzene series, said mixture containing between 1 and 10% of said body.

8. Process for the manufacture of an aliphatic anhydride, which comprises subjecting to thermal decomposition a vaporous mixture comprising an aliphatic acid and a lower aliphatic acid ester of phenol, said mixture containing between 1 and 10% of said ester.

9. Process for the manufacture of an aliphatic anhydride, which comprises subjecting to thermal decomposition a vaporous mixture comprising an aliphatic acid and phenol, said mixture containing between 1 and 10% of phenol.

10. Process for the manufacture of an aliphatic anhydride, which comprises subjecting to thermal decomposition, at temperatures of about 300 to 700 C., a vaporous mixture comprising an aliphatic acid and 1 to 10% of phenol.

11. Process for the manufacture of an aliphatic anhydride which comprises subjecting a vaporous mixture of an aliphatic acid and phenol containing 5% phenol to thermal decomposition at a temperature between 400 and 600 C.

15. Process for the manufacture of acetic an hydride, which comprises subjecting the vapor of acetic acid to thermal decomposition in presence of a lower aliphatic acid ester of a monohydric phenol of the benzene series.

16. Process for the manufacture of acetic an:

hydride, which comprises subjecting the vapor of acetic acid to thermal decomposition in presence of a lower aliphatic acid ester of phenol.

17. Process for the manufacture of acetic anhydride, which comprises subjecting the vapor of acetic acid to thermal decomposition in presence of phenol acetate.

18. Process for the manufacture of acetic anhydride, which comprises subjecting to thermal decomposition a vaporous mixture comprising acetic acid and a body selected from the group consisting of monohydric phenols of the benzene series and their lower aliphatic acid esters, said mixture containing between 1 and 10% of said body.

19. Process for themanufacture of acetic anhydride, which comprises subjecting to thermal decomposition a vaporous mixture comprising acetic acid and phenol acetate, said mixture containing between 1 and 10% of the phenol acetate.

20. Process for the manufacture of acetic anhydride, which comprises subjecting to thermal decomposition a vaporous mixture comprising acetic acid and phenol, said mixture containing between 1 and 10% of phenol.

21. Process for the manufacture of acetic anhydride, which comprises subjecting to thermal decomposition, at temperatures of about 300 to 700 C., a vaporous mixture comprising acetic acid and 1 to 10% of abody selected from the group consisting of phenol and its lower aliphatic acid esters.

22. Process for the manufacture of acetic'anhydride which comprises subjecting a vaporous mixture of acetic acid and phenol containing 5% phenol to thermal decomposition at a temperature between 400 and 600 C.

HENRY DREYFUS.